JPS5867608A - Bactericide - Google Patents

Abstract

Fungicides containing an aqueous solution of a salt of 2-(methoxy-carbonylamino)-benzimidazole and a weak acid, and methods of controlling fungi and preserving wood using these solutions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is intended for the protection of plants against plant diseases containing salts of 2-(methoxy-carbonylami/)-benzimidazole together with a weak acid, such as a sulfonic acid, and for the protection of wood. Concerning fungicides for protection.

2-(Methoxy-carbonylamino)-benzimidazole (BOM) f)r Has bactericidal activity.

Known (R, Wegler),
``Hemi-der-Bufranzenschutz-Land-Sietolinksbekenpfungsmitte-l.
hemie der Pflanzenscutz -
und SchKdlingabe-kMmpfun
gsmittel)”, Volume 4, pp. 180 et seq.

Springer-Verlag (
Berlin)), 1977; Patent Application Publication No. 204006913 of the Federal Republic of Germany). Furthermore, it is possible to use the salts of this active substance in the form of aqueous solutions with a pH value of less than 4 together with salts with an ionization constant of more than 1.times.10.sup.6 for controlling fungal plant diseases.

publicly known (Federal Republic of Germany Patent Application No. 1792)
688 specification).

By the way, an aqueous solution of a salt of 2-(methoxy-carbonylamino)-benzimidazole, obtained using a weak acid, is suitable for protecting wood from destruction by fungi or bacteria and is useful against phytopathological fungi. It has been found that the plant has an extremely good effect on the plants and surprisingly exhibits good plant 1:3 tolerability.

A weak acid is a weak inorganic or organic acid. Such an acid is 9
For example, fluoroboric acid (HBF), hexafluorosilicic acid, monoesters or diesters of phosphoric acid and alcohols (for example butanol or polyethylene glycol) or sulfonic acids.

For example, sulfamic acid or aliphatic or aromatic sulfonic acids, in particular aromatic sulfones which can have other groups in the organic radical (for example phenyl), such as hydroxyl, amide or carboxyl groups. Acids (eg phenylsulfonic acid) 1 For example 4-phenolsulfonic acid. Aromatic sulfonic acids 2 having more than one sulfonic acid group in the molecule, for example the corresponding di- or trisulfonic acids, may also be used. When using bioactive acids.

The protective action of the solution can be extended, thus, for example, fluoroboric acid contains fluorine or boron, which additionally has a bactericidal action. Preferably.

BOM of 4-phenolsulfonic acid Al in N.

The aqueous solution of this salt is BOM in terms of BOM without acid.
It contains from 0.01 to 5% by weight, especially from 0.025 to 1% by weight. The pH value of this solution can vary within wide ranges; it preferably lies between 1.5 and 4.5. B
The molar ratio of OM and acid is 9, e.g. 1:1.

:2.5. Preferably 1=2. Excess amount of high acid.

There is no harm provided that the pH value of the aqueous solution is within the above range.

The solution can contain, in addition to the salt of 2-(methoxy-carbonylamino)-benzimidazole, further components 9, such as corrosion inhibitors, wetting agents, dyes or additionally active substances with bactericidal action.

The novel fungicides are suitable, for example, as storage protectants or anti-blue agents.

Wood consists of the wood itself as well as its metabolic rate.

For example, wood chips, pulp or intermediates and products in the production of paper from wood. Furthermore, this disinfectant is suitable for protecting industrial materials 1 such as paper pulp, water in cooling systems, paints against fungal infections.

The salt of 2-(methoxy-carbonylamino)-benzimidazole is mixed into a solution of about 30-70% by weight of the corresponding acid in water under BOM tl-stirring and the mixture is added to BOM tl-stirring.
Obtained by stirring until the OM goes into complete solution. A clear solution generally results.

The solution solidifies after 1-2 hours under crystal separation. If salt should not be crystallized, 1. <The solution is
It can be used as such.

This salt can be isolated as a solid substance; it shows good solubility in water. Preferably, the salt is
It is obtained in the form of its aqueous solution and used in this form without isolating the solid substance into intermediates. This salt has, for example, the following composition: BOM 1 mol 4-7 eth/- sulfonic acid 2 mol BOM 1 mol sulfamic acid 2 mol BOM 1 mol HBF, 2 mol Example 1 4-7 eth/- 2 moles of rusulfonic acid are prepared as a 60% aqueous solution; to this is then added 1 mole of 2-(methoxy-carbonylamino)-benzimidazole under stirring. 2-(Methoxy-carbonylami/)-benzimidazole dissolves under slight heating. The clear, slightly viscous solution becomes solid after 1-2 hours; the product can be dried, ground and used without further treatment to obtain an aqueous solution of the salt. This dry salt has a melting point of 2
It has a temperature of 00°C.

Example Fill EOM into a vacuum kneading chamber of appropriate size.

Sulfamic acid (,,NH2so,a) in a molar ratio of 1:
Dry mix in Step 2 (about 15 minutes). Continue to add distilled water (
10% (wt%) of the mixture is added and the paste that forms is kneaded for at least 30 minutes. Since this reaction is exothermic, it can be cooled if necessary depending on the amount of the mixture.

Subsequently, the kneading machine is evacuated and the water is discharged while kneading. Depending on the quantity, the mixture is advantageously heated to 40°C. After about 1 hour, the reaction mixture is dry.

It is present in the kneading machine in the form of fine particles.

The BOM-sulfamic acid salt thus obtained (melting point 1
75°C) is clearly soluble in water.

Due to the significant water solubility of the salt, the active substance 2-(methoxycarbonylamino)-benzimidazole is generally used as a suspension of the corresponding active substance V of various particle sizes for the plant part to be protected. can be distributed better than in the case of Furthermore, the absorption of active substances in the roots, leaves, and stem portions is similar to that of the cutting, and the osmotic transfer effect is significantly affected.

Diseases caused by the following fungi can be controlled with the fungicide according to the present invention, such as grapes, apples, cucurbits, and ornamental plants.9 For example, roses,
Botrytis cinere, a, true downy mildew of zinnia and oleander, Botrytis cinere, a, botrytis of grapes, bell peppers, strawberries and hops;
Sclerotium fungus of rapeseed, 5clerot4-n
ia sclerotiorum, wheat 0e
rcosporellaherpotricho=id
es, wheat blight 141. j Septor
ianoaorum, 7thalium, 0er
coapora kiki-chii, O,Bo
jnae, Diaporthe phase
-olorum, Dice Phomopais,
Groundnut Oe-rcospora persona
ta; apple and pear Venturia 1
naequal soil S, elm oeratacyIlyt
Us-tilagOQ is a fruit rot disease caused by the spp. and the amount of active substance is 0.05-3 kg/ha or more. The dipping or injection solutions contain from 0.025 to 1% by weight of active substance, calculated as, for example, 2-(methoxy-carbonylamino)-benzimidazole.

The use for protecting wood can be carried out, for example: a) by spraying the wood with a solution b) by immersing the wood in the solution C) by container pressure impregnation of the wood d) by washing the wood By application.

Wood metabolites 1, for example wood chips, valves, and other industrial products susceptible to fungal and/or bacterial infections 1, used in accordance with industrial processes, for example in the case of intermediate products in paper production .

The action of fungicides within the scope of wood protection is primarily related to: a) fungi (e.g. Aspergillus ni
ger) b) Rot fungi (e.g. Ohaatom)
ium globosum)C) Blue stain bacteria (e.g.
Pulularia pullulans ) d)
Bacteria and, at high concentrations, also associated with: e) wood-destroying fungi (e.g. 5erpula lacryma);
ns).

Its use for protecting wood shows amazing benefits.

1) The solution penetrates well into wood or wood metabolites.

2) Wood glue that prevents aqueous solution from penetrating into wood is
Not caused by acidic solutions.

3) The pH value of the infiltrated solution is increased by the buffering action of the wood, so that the active substance is freed from the acidic solution.

The following description of fungicides that can be combined with the fungicides according to the invention details, but does not limit, the method of combination. This is the case, for example, for primary disinfectants: Sulfur.

Dithiocarbamates and their derivatives 1 eg iron dimethyldithiocarbamate), zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate or zinc ethylenebisdithiocarbamate.

Tetramethylthiuramide sulfide.

An ammonia complex compound of sub-G-(N I N-ethylene-bis-dithiocarbamate) and N,N'-polyethylene-bis-(thiocarbamoyl cudisulfide).

Ni-(NtN'-propylene-bis-dithiocarbamate).

Ammonia complexes of zinc-(N,N'-propylene-bis-dithiocarbamate) and N,N'-propylene-bis(thiocarbamoyl)-disulfide; nitro derivatives 9 such as dinitro-(1-methylhebutyl)-phenylcrot Nate.

2-s-butyl-4,6-sinitrophenyl-3.3-
Dimethyl acrylate.

2-s-7'thyl-4,6-sinitrophenyl-isopropyl carbonate; Heterocyclics 1 such as N-(1,1,2,2-tetrachloroethylthio)-tetrahydro7talimide.

N-) Lichloromethylthiotetrahydrophthalimide
Do.

N-) dichloromethylthio 7-talimide.

2-Heptadecyl-2-imidacillin-acetate.

2.4-dichloro-6-(o-chloroanilino)-s-
) riazine.

0.0-Diethyl-phthalimidophosphonothioate.

5-amino-1-(bis-(dimethylamino)-phosphinyl)-3-7enyl-1.2',4-triazole.

5-ethoxy-3-trichloromethyl-1,2°4-thiadiazole, □2,3-dicyano-1,4-dithioanthraquinone.

Methyl 2-thio-1,3-dithio-(a,5-b)-dacylcarbamate.

N゛ 2-Methoxyluponylaminoben imidazole.

N゛ 2-Rhodanmethylthio-bendothiazole.

4-(2-chlorophenylhydrazono)-3-methyl-
5-Inxacilone.

Pyrin-2-thio-1-oxide.

8-Hydroxyquinoline or its copper salt.

2.3-dihydro-5-carboxyanilide-6-methyl-1,4-oxathiine-4,4-dioxide.

2.3-Dihydro-5-carboxyanilide-piperazine-1,4-diyl-bis-(1-(2,2,2-)lichloroethyl)-formamide).

2-(thiazolyl-(4))-benzimidazole 5-
Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine.

Bis-(p-chlorophenyl)-pyridine methanol.

1.2-Su(3-ethoxycarbonyl-2-thioureido)-penzole.

1.2-Bis-(3-methoxycarbonyl-2-thioureido)-penzole and other substances 1 such as dodecylguanidine acetate.

3-(3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl)-glutarimide.

Hexachlorbenzole.

N-dichlorofluoromethylthio-N,N-dimethyl-
N-phenyl-sulfuric diamide.

2.5-Dimethyl-furan-3-carboxylic acid anilide.

2.5-Dimethyl-furan-3-carboxylic acid-cyclohexylamide.

2-Cyan-N-(ethylaminocarbonyl)-2-(
methoxyimino)-acetamide.

2~Methyl-benzoic acid-anilide.

2-Iodo-benzoic acid-anilide.

1-(3,4-dichloroanilino)-1-formylamino-2,2,2-)dichloroethane.

2.6-Simethyl-N-)lysosyl-morpholine or a salt thereof.

2.6-Dimethyl-N-cyclododecyl-morpholine is its salt.

DL-Methyl-N-(2,6-cymethyl-7enyl)-
N-furoyl(2)-alaninate.

DL-N-(2,6-dimethyl-phenyl)-u-(2
-methoxyacetyl)-alanine-methyl ester.

5-Nitro-isophthalic acid-di-isopropyl ester.

1-(IJ, 21, 41-triazolyl-1
)'-(4'-Chlorphe/xy)-3,3-dimethylbutan-2-one.

1-(1”, '2', 4'-)riazolyl-
1) -1-(41-'Chlorphenoxy)-3,3-dimethylbutan-2-ol.

N-(2,6-dimethylphenyl)-N-chloroacetyl-D, L-2-aminobutyrolactone.

N-(n-propyl)-N-(2,4,6-dolychlor7e/xyethyl)-NI-imidazolylurea.

Example 3 Botrytis oiner, a fungus that causes gray mold on paprika
4 to 4 to 4 to 4 to 4 to 4 to 4 to 4 to 4 to
After good development of 5 leaves, it contains 0.025%, 0.05% and 0.1% of active substance calculated as 2-(methoxy-carbonylamino)-benzimidazole. The aqueous salt solution according to Example 1 is sprayed until drippings. After the spray coating has dried.

The plants are sprayed with a conidial suspension of the fungus Botrytis cinθrea and placed in a chamber with high air humidity at 22°C to 24°C. After 5 days, the disease had developed to such an extent that the resulting foliage necrosis covered most of the foliage relative to the untreated control plants. The bactericidal effect is evaluated as follows: 20 means no bacterial infection, and up to 5 means no infection.

Morbidity of foliage after spraying with the following percentages of active substanceExample/BOM fortune of Example 2 Example q Fungus Sclerophoma pityo that discolors wood
phila and Pu1lularia pullula
The effect of the active substance described in Example/4ζ on ns was tested. To conduct this test, a piece of pine wood was
In the process, the aqueous solution containing 0.25%, 0.5% and 1% of the effective substance to the BOM was added to the wood hole area 11r? Hit 2
X 100 g was applied.

A control surface is coated with the same amount of linseed oil varnish. After applying a colorless alkyl resin lacquer, the pieces of wood were exposed to nature in the open air for 6 months and then placed in a germ-enriching dish for fungal testing. After the end of the test, the control surface of the test wood pieces had an average of 90% 5cle, rophoma
pityophila and Pu1lularia pu
K) for the growth of ll-ullns! /It was strange. The test results are summarized in the first table.

Q, 5 0, 1.0 0 3 more than '3
more than 2.0 0 3
More than 0 - No signs of blue stain infection 1-3 Transition stage until complete blue stain infection The composition of the wood protectant is detailed in the following examples.

Example j BOM 0.40% (wt%)
4-phenolsulfonic acid 0.80% vs. r! l:i
Dye (taldrazine yellow) -0.20% rot!
Inhibitor (benzotriazole) 0.20% water
98.40
% Example 6 BOM 0.40% 4-phenolsulfonic acid 0.80% Corrosion inhibitor (benzotriazole) 0.20% Water
98.60% Example 7 BOM 0.40% Fluoroboric acid (HBF,) 0.30% Wet Acid 1 (p-7 Nylphenol Ethoxylate (Ethoxyl Number = 7-12)) 1.00% Dye ( Taldrazine Yellow) 0.50% water
97.80% patent applicant Basfachchengesellschaft representative patent attorney 1) Tomaku Tomari

Claims (1)

[Claims] (1) A disinfectant comprising an aqueous solution of a salt of 2-(methoxy-carbonylamino)-benzimidazole together with a weak acid. (J) The fungicide according to claim (1), characterized in that 2-(methoxy-carbonylamino)-benzimidazole is present together with sulfonic acid. (3) The fungicide according to claim (c), characterized in that it contains a salt of 2-(methoxy-carbonylamino)-benzimidazole together with 4-phe/-lsulfonic acid or sulfamic acid.